WO2023120596A1 - Masterbatch, preform, blow-molded bottle, beverage product, film, method for producing preform, and method for producing blow-molded bottle - Google Patents

Abstract

The purpose of the present disclosure is to provide: a masterbatch which, for PET/PEF blend molding, does not require extra molding time, can achieve stabilized molding, and further, makes it possible to obtain a good quality molded article; a preform; a blow-molded bottle; a film; a beverage product; a method for producing a preform; a method for producing a blow-molded bottle; and a method for producing a film.　A masterbatch according to the present disclosure contains a polyester resin (A) comprising a terephthalic acid-derived structural unit (A-1) and an aliphatic diol-derived structural unit (A-2), and a polyester resin (B) comprising a 2,5-furandicarboxylic acid-derived structural unit (B-1) and a 1,2-ethanediol-derived structural unit (B-2). The content ratio of the polyester resin (B), determined by (formula 1), is 45 mass% to 90 wt%, and the intrinsic viscosity (IV value), measured under (condition 1), is 0.50 dl/g to 1.20 dl/g.

Description

MASTERBATCH, PREFORM, BLOW-MOLDED BOTTLE, BEVERAGE PRODUCTS, FILM, PREFORM MANUFACTURING METHOD AND BLOW-MOLDED BOTTLE MANUFACTURING METHOD

The present disclosure relates to a masterbatch containing, for example, polyethylene terephthalate resin (hereinafter also referred to as PET resin or PET) and polyethylene furanoate resin (hereinafter also referred to as PEF resin or PEF). Furthermore, a preform molded using the masterbatch, a bottle obtained by blow molding the preform, a beverage product in which the bottle is filled with a beverage, a film using the masterbatch, a method for producing the preform, and the blow It relates to a method for manufacturing molded bottles.

Conventionally, PET has excellent transparency, mechanical properties, and gas barrier properties, and has been widely used as a film for beverage containers such as carbonated drinks, fruit juices, and water, display members, food packaging members, and construction materials. ing. Furthermore, PEF is expected as a substitute polyester for PET.

For example, a PEF-containing preform for manufacturing a plastic container by stretch blow molding has been disclosed (see, for example, Patent Document 1). Specifically, a container having high mechanical strength and high barrier properties can be obtained by producing a preform having a viscosity of 0.75 dl/g to 0.9 dl/g and a water content of less than 50 ppm. is described. For film applications, a biaxially stretched film using PEF has been disclosed (see Patent Document 2).

Japanese Patent Publication No. 2018-510800 Japanese Patent Publication No. 2017-536427

PEF has higher heat resistance and gas barrier properties than PET. It is expected that a container that can be filled with contents such as various beverages sold hot can be obtained.

However, in the blend molding of PET and PEF, which have different heat resistance temperatures, there is a problem that the kneading time required to make the different resins compatible and the molding quality due to the difference in the crystallization speed during the molding process, especially during cooling. There are problems that lead to degradation. These problems lead to prolonged molding time, unstable molding, and deterioration in the quality of molded products.

Therefore, in the blend molding of PET and PEF, the masterbatch and the printer realize that the molding is stabilized without prolonging the molding time, and the quality of the resulting molded product is improved. It is an object of the present invention to provide a method for manufacturing reformed, blow-molded bottles, films, beverage products, preforms, and methods for manufacturing blow-molded bottles and films.

As a result of extensive studies by the present inventors, when PET, which is the main material, is blended with PEF as an additive, by using PEF as an additive in the main material and making a masterbatch at a predetermined high concentration, it is possible to achieve a short time. The inventors have found that a blended polyester molded product can be obtained that is capable of compatibilization and kneading at a high temperature and that is excellent in molding quality and production suitability, and completed the present invention. That is, the masterbatch according to the present invention comprises a polyester resin (A) having a terephthalic acid-derived structural unit (A-1) and an aliphatic diol-derived structural unit (A-2), and a 2,5-flange A polyester containing a structural unit (B-1) derived from a carboxylic acid and a polyester resin (B) having a structural unit (B-2) derived from 1,2-ethanediol, and obtained by (Equation 1) The content of the resin (B) is 45% by mass to 90% by weight, and the intrinsic viscosity (IV value) measured according to (Condition 1) is 0.50 dl/g to 1.20 dl/g. .
(Formula 1) content of polyester resin (B) (% by mass) = content of polyester resin (B) / (content of polyester resin (A) + content of polyester resin (B))
(Condition 1) 0.25 g of the masterbatch is dissolved in 50 ml of a mixed solvent of phenol/1,1,2,2-tetrachloroethane = 50/50 (weight ratio), and measured at 30°C using an Ubbelohde viscometer. The Huggins constant is 0.32.

The masterbatch according to the present invention includes forms for molding pressure-resistant bottles, bottles for heated sales, or heat-resistant bottles.

The method for producing a molded article according to the present invention includes a polyester resin (A) having a terephthalic acid-derived structural unit (A-1) and an aliphatic diol-derived structural unit (A-2), and a 2,5- It contains a structural unit (B-1) derived from furandicarboxylic acid and a polyester resin (B) having a structural unit (B-2) derived from 1,2-ethanediol, and is obtained by (Equation 1) A step of producing a masterbatch having a polyester resin (B) content of 90% by mass or less and an intrinsic viscosity (IV value) measured according to (Condition 1) of 0.50 dl / g to 1.20 dl / g. and a step of separately melt-kneading the masterbatch and the polyester resin (A) to form a molded body.
(Formula 1) content of polyester resin (B) (% by mass) = content of polyester resin (B) / (content of polyester resin (A) + content of polyester resin (B))
(Condition 1) 0.25 g of the masterbatch is dissolved in 50 ml of a mixed solvent of phenol/1,1,2,2-tetrachloroethane = 50/50 (weight ratio), and measured at 30°C using an Ubbelohde viscometer. The Huggins constant is 0.32.

In the method for producing a molded body according to the present invention, the masterbatch is a masterbatch in which the content of the polyester resin (B) determined by (Equation 1) is 45% by mass to 90% by weight, and the molded body is The step of molding includes a step of blending the masterbatch and the polyester resin (A) to mold a preform for a bottle.

The method for manufacturing a blow-molded bottle according to the present invention is characterized by having a step of molding a bottle by blow-molding the preform obtained by the method for manufacturing a molded body according to the present invention.

The preform according to the present invention comprises a polyester resin (A) having a terephthalic acid-derived structural unit (A-1) and an aliphatic diol-derived structural unit (A-2),
A polyester resin (B) having a structural unit (B-1) derived from 2,5-furandicarboxylic acid and a structural unit (B-2) derived from 1,2-ethanediol,
A bottle preform made of a resin composition having a polyester resin (B) content of 5 to 25% by mass as determined by (Equation 1),
Except that the intrinsic viscosity (IV value) measured under (Condition 2) is 0.65 dl / g or more and 1.00 dl / g or less, and the luminous flux is narrowed to 7.0 mm square, JIS K 7136: 2000 "Plastic- It is characterized by having a haze value of 0.1 to 8% as measured according to "Method for Determining Haze of Transparent Materials".
(Formula 1) content of polyester resin (B) (% by mass) = content of polyester resin (B) / (content of polyester resin (A) + content of polyester resin (B))
(Condition 2) 0.25 g of a sample cut from the preform was dissolved in 50 ml of a mixed solvent of phenol/1,1,2,2-tetrachloroethane = 50/50 (weight ratio), and measured at 30°C using an Ubbelohde viscometer. , and the Huggins constant is 0.32.

The blow-molded bottle according to the present invention comprises a polyester resin (A) having a structural unit (A-1) derived from terephthalic acid and a structural unit (A-2) derived from an aliphatic diol, and 2,5-furandicarboxylic A polyester resin containing a structural unit (B-1) derived from an acid and a polyester resin (B) having a structural unit (B-2) derived from 1,2-ethanediol, and obtained by (Equation 1) A blow-molded bottle made of a resin composition in which the content of (B) is 5 to 25% by mass, wherein the intrinsic viscosity (IV value) measured according to (Condition 3) is 0.65 dl/g or more and 1.00 dl/ g or less, and the haze value measured according to JIS K 7136: 2000 "Plastics - Determination of haze of transparent materials" is 0.1 to 20%, except that the luminous flux is narrowed to 7.0 mm square. Characterized by
(Formula 1) content of polyester resin (B) (% by mass) = content of polyester resin (B) / (content of polyester resin (A) + content of polyester resin (B))
(Condition 3) 0.25 g of a sample cut from a blow-molded bottle was dissolved in 50 ml of a mixed solvent of phenol/1,1,2,2-tetrachloroethane = 50/50 (weight ratio), and measured at 30 using an Ubbelohde viscometer. The Huggins constant, measured in °C, is taken to be 0.32.

The blow-molded bottle according to the present invention is preferably a pressure-resistant bottle for filling with a carbonate-containing liquid. INDUSTRIAL APPLICABILITY The blow-molded bottle according to the present invention is excellent in pressure resistance and heat resistance, and is suitable for filling with a carbonate-containing liquid. Moreover, it is suitable also regarding recyclability.

The blow-molded bottle according to the present invention is preferably a bottle for filling hot sales bottles or a heat-resistant bottle for filling at high temperature. The blow-molded bottle according to the present invention has excellent heat resistance and high gas barrier properties, and can be used as a container when sold as a hot beverage at 60°C, for example, or when filled at a liquid temperature of 90°C, for example. Deformation is suppressed, and as a result, the degree of freedom in container design is high, and reduction in container weight and reduction in CO ₂ emissions can be realized. Moreover, it is suitable also regarding recyclability.

The beverage product according to the present invention is characterized by filling the molded bottle according to the present invention with a beverage.

The method for producing a molded article according to the present invention includes a form in which the molded article is a film.

The film according to the present invention includes a polyester resin (A) having a terephthalic acid-derived structural unit (A-1) and an aliphatic diol-derived structural unit (A-2), and a 2,5-furandicarboxylic acid-derived and a polyester resin (B) having a structural unit (B-1) and a structural unit (B-2) derived from 1,2-ethanediol, and the polyester resin (B ) content is 1 to 90% by mass, and the intrinsic viscosity (IV value) measured according to (Condition 4) is 0.50 dl / g or more and 1.00 dl / g or less , The haze value measured according to JIS K 7136: 2000 "Plastics - Determination of haze of transparent materials" is 0.01 to 6.0%, except that the luminous flux is narrowed to 7.0 mm square. do.
(Formula 1) content of polyester resin (B) (% by mass) = content of polyester resin (B) / (content of polyester resin (A) + content of polyester resin (B))
(Condition 4) 0.25 g of the film is dissolved in 50 ml of a mixed solvent of phenol/1,1,2,2-tetrachloroethane = 50/50 (weight ratio), and measured at 30°C using an Ubbelohde viscometer. The constant is 0.32.

According to the present disclosure, in blend molding of PET and PEF, a masterbatch that realizes stable molding without prolonging the molding time and further improving the quality of the resulting molded product, Preforms, blow-molded bottles, films, beverage products, methods of making preforms, methods of making blow-molded bottles, and methods of making films can be provided. The resulting molded product has high molding quality and high productivity.

It is a schematic diagram explaining a haze measuring method of a preform.

Although the embodiments of the present invention will be described with reference to the drawings, the present invention is not interpreted as being limited to these descriptions. Various modifications may be made to the embodiments as long as the effects of the present invention are achieved.

[Master Badge]
The masterbatch according to the present embodiment comprises a polyester resin (A) having a structural unit (A-1) derived from terephthalic acid and a structural unit (A-2) derived from an aliphatic diol, and 2,5-furandicarboxylic A polyester resin containing a structural unit (B-1) derived from an acid and a polyester resin (B) having a structural unit (B-2) derived from 1,2-ethanediol, and obtained by (Equation 1) The content of (B) is 90% by mass or less.
(Formula 1) content of polyester resin (B) (% by mass) = content of polyester resin (B) / (content of polyester resin (A) + content of polyester resin (B))

In the present specification, the term "structural unit derived from ..." refers to a structural unit derived from the monomer (monomer) and incorporated into the polymer polyester. Hereinafter, "structural unit derived from ..." is simply referred to as "unit" or "structural unit", for example, "structural unit derived from diol" is "diol unit" or "diol structural unit", " "Structural unit" is "terephthalic acid unit" or "terephthalic acid structural unit", "structural unit derived from 2,5-furandicarboxylic acid" is "2,5-furandicarboxylic acid unit" or "2,5-furandicarboxylic acid "structural unit" and "structural unit derived from 1,2-ethanediol" are sometimes referred to as "1,2-ethanediol unit" or "1,2-ethanediol structural unit", respectively.

As used herein, the term "main structural unit" refers to a structural unit that accounts for the largest proportion of the "structural unit", and is usually 50 mol% or more, preferably 70 mol% of the structural unit. Above, the structural unit accounts for more preferably 80 mol % or more, still more preferably 90 to 100 mol %.

(polyester resin)
A polyester resin has a dicarboxylic acid unit and a diol unit, and the polyester resin (A) has a terephthalic acid unit as the main structural unit of all the dicarboxylic acid units that constitute the polyester, and an aliphatic diol unit that constitutes the polyester. It is preferably the main structural unit of all diol units. It is more preferable to use ethylene glycol units as main structural units of all diol units constituting the polyester. In the polyester resin (B), 2,5-furandicarboxylic acid units are the main structural units of all dicarboxylic acid units constituting the polyester, and 1,2-ethanediol units are the main structural units of all diol units constituting the polyester. It is preferably used as the main structural unit.

The polyester resin (A) includes a form that is a PET resin. Moreover, the polyester resin (B) includes a form that is a PEF resin. Next, the polyester resin (A) and polyester resin (B) will be described in more detail.

(Polyester resin (A))
<Dicarboxylic acid structural unit>
The polyester resin (A) contains a structural unit (A-1) derived from terephthalic acid as a dicarboxylic acid structural unit. By including the structural unit (A-1) derived from terephthalic acid, the glass transition temperature is increased, the heat resistance is improved, and the gas barrier property is also improved. The polyester resin (A) preferably has a structural unit (A-1) derived from terephthalic acid as a main dicarboxylic acid unit. That is, the structural unit (A-1) derived from terephthalic acid is usually 50 mol% or more, preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 100 mol% of all dicarboxylic acid structural units. It is preferably contained in an amount of 90 to 100 mol %.

A dicarboxylic acid unit other than a terephthalic acid unit (also referred to as a "dicarboxylic acid other than terephthalic acid") may be included as a dicarboxylic acid unit. Dicarboxylic acids other than terephthalic acid include aliphatic dicarboxylic acids and aromatic dicarboxylic acids other than terephthalic acid. Aliphatic dicarboxylic acids include chain aliphatic dicarboxylic acids such as oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dimer acid and dodecanedioic acid; cycloaliphatic dicarboxylic acids such as 1,6-cyclohexanedicarboxylic acid; acid. Aromatic dicarboxylic acids other than terephthalic acid include isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid and the like.

In the case where a dicarboxylic acid structural unit other than terephthalic acid is contained as a dicarboxylic acid structural unit, the dicarboxylic acid structural unit other than terephthalic acid contained may be of only one type or two or more types in any combination and ratio. good. In the case where the polyester resin (A) contains a dicarboxylic acid structural unit other than terephthalic acid, the content is preferably small in order to sufficiently obtain the above effects due to the inclusion of the terephthalic acid structural unit. On the other hand, from the point of view of excellent flexibility and the like, a large number is preferable. Therefore, when a dicarboxylic acid structural unit other than terephthalic acid is contained, the content thereof is usually 10 mol% or more, preferably 20 mol% or more, more preferably 30 mol% or more, based on 100 mol% of all dicarboxylic acid structural units. and its upper limit is usually 50 mol %.

<Diol Structural Unit>
In this embodiment, a structural unit (A-2) derived from an aliphatic diol is included as a diol structural unit. Including the structural unit (A-2) derived from the aliphatic diol improves the heat resistance and gas barrier properties of the bottle produced using the polyester. In addition, as the diol structural unit, a diol other than an aliphatic diol (hereinafter also referred to as "a diol other than an aliphatic diol") may be included as a structural unit. mentioned. Aliphatic diols include 2,2′-oxydiethanol, 2,2′-(ethylenedioxy)diethanol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,5 -Pentanediol, 1,6-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, ethylene glycol, diethylene glycol, triethylene glycol, isosorbide and the like. Examples of aromatic diols include xylylene glycol, 4,4'-dihydroxybiphenyl, 2,2-bis(4'-hydroxyphenyl)propane, 2,2-bis(4'-β-hydroxyethoxyphenyl ) propane, bis(4-hydroxyphenyl)sulfone, bis(4-β-hydroxyethoxyphenyl)sulfone and the like. When the polyester resin (A) contains diol structural units of aliphatic diols, the diols other than the aliphatic diols may be contained alone or in any combination and ratio.

The polyester resin (A) preferably has ethylene glycol-derived structural units (A-2) as main diol structural units. That is, the ethylene glycol structural unit is usually 50 mol% or more, preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 100 mol% of all diol structural units contained in the polyester resin (A). From the viewpoint of improving heat resistance and gas barrier properties, it is preferable to contain 90 mol % or more, particularly preferably 100 mol %.

(Polyester resin (B))
<Dicarboxylic acid structural unit>
The polyester resin (B) contains a structural unit (B-1) derived from 2,5-furandicarboxylic acid as a dicarboxylic acid structural unit. By containing the structural unit (B-1) derived from 2,5-furandicarboxylic acid, the glass transition temperature is increased, the heat resistance is improved, and the gas barrier property is also improved. The polyester resin (B) preferably has a structural unit (B-1) derived from 2,5-furandicarboxylic acid as a main dicarboxylic acid unit. That is, the structural unit derived from 2,5-furandicarboxylic acid is usually 50 mol% or more, preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 100 mol% of all dicarboxylic acid structural units. It is preferably contained in an amount of 90 to 100 mol %.

As dicarboxylic acid units, dicarboxylic acid units other than 2,5-furandicarboxylic acid units (also referred to as "dicarboxylic acids other than 2,5-furandicarboxylic acid") structural units may be included. Dicarboxylic acids other than 2,5-furandicarboxylic acid include aliphatic dicarboxylic acids and aromatic dicarboxylic acids. Aliphatic dicarboxylic acids include chain aliphatic dicarboxylic acids such as oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dimer acid and dodecanedioic acid; cycloaliphatic dicarboxylic acids such as 1,6-cyclohexanedicarboxylic acid; acid. Examples of aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, and diphenyldicarboxylic acid. Among these dicarboxylic acids, aliphatic dicarboxylic acids are preferable, and chain aliphatic dicarboxylic acids are more preferable, because they are excellent in flexibility.

In the case where a dicarboxylic acid structural unit other than 2,5-furandicarboxylic acid is included as a dicarboxylic acid structural unit, the dicarboxylic acid structural unit other than 2,5-furandicarboxylic acid contained may be one type or two types. The above may be included in any combination and ratio. In the case where the polyester resin (B) contains a dicarboxylic acid structural unit other than 2,5-furandicarboxylic acid, the content of the dicarboxylic acid structural unit is such that it is easy to sufficiently obtain the above effects due to the inclusion of the 2,5-furandicarboxylic acid structural unit. less is preferable. On the other hand, from the point of view of excellent flexibility and the like, a large number is preferable. Therefore, when a dicarboxylic acid structural unit other than 2,5-furandicarboxylic acid is contained, the content thereof is usually 10 mol% or more, preferably 20 mol% or more, more preferably 20 mol% or more, based on 100 mol% of all dicarboxylic acid structural units. is preferably 30 mol % or more, and its upper limit is usually 50 mol %.

<Diol Structural Unit>
In this embodiment, a structural unit (B-2) derived from 1,2-ethanediol is included as a diol structural unit. By including the structural unit (B-2) derived from 1,2-ethanediol, the heat resistance and gas barrier properties of bottles produced using polyester are improved. In addition, as a diol structural unit, a diol other than 1,2-ethanediol (hereinafter also referred to as "a diol other than 1,2-ethanediol") may be included as a structural unit. Diols include aliphatic diols and aromatic diols excluding 1,2-ethanediol. Aliphatic diols other than 1,2-ethanediol include 2,2′-oxydiethanol, 2,2′-(ethylenedioxy)diethanol, 1,3-propanediol, 1,2-propanediol, 1,2-propanediol, 4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, ethylene glycol, diethylene glycol, triethylene glycol, isosorbide and the like. Examples of aromatic diols include xylylene glycol, 4,4'-dihydroxybiphenyl, 2,2-bis(4'-hydroxyphenyl)propane, 2,2-bis(4'-β-hydroxyethoxyphenyl ) propane, bis(4-hydroxyphenyl)sulfone, bis(4-β-hydroxyethoxyphenyl)sulfone and the like. When the polyester resin (B) contains a diol structural unit other than 1,2-ethanediol, the diol other than 1,2-ethanediol may be used alone or in any combination and ratio. may

The polyester resin (B) preferably has a structural unit (B-2) derived from 1,2-ethanediol as a main diol structural unit. That is, the 1,2-ethanediol structural unit is usually 50 mol% or more, preferably 70 mol% or more, more preferably 80 mol% or more in 100 mol% of all diol structural units contained in the polyester resin (B). , more preferably 90 mol % or more, and particularly preferably 100 mol %, from the viewpoint of improving heat resistance and gas barrier properties.

(Other Copolymerization Components of Polyester Resin (A) and Other Copolymerization Components of Polyester Resin (B))
The polyester resin (A) and the polyester resin (B) may contain structural units derived from copolymerization components other than dicarboxylic acid and diol. Other copolymerization components include compounds containing trifunctional or higher functional groups.

Examples of compounds having trifunctional or higher functional groups include trifunctional or higher polyhydric alcohols, trifunctional or higher polycarboxylic acids (or their anhydrides, acid chlorides, or lower alkyl esters), trifunctional or higher hydroxycarboxylic acids. Acids (or their anhydrides, acid chlorides, or lower alkyl esters), tri- or higher functional amines, and the like.

Examples of trifunctional or higher polyhydric alcohols include glycerin, trimethylolpropane, and pentaerythritol. One of these may be used alone, or two or more may be used in any combination and ratio.

Tri- or more functional polycarboxylic acids or anhydrides thereof include trimesic acid, propanetricarboxylic acid, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, cyclopentatetracarboxylic anhydride and the like. . One of these may be used alone, or two or more may be used in any combination and ratio.

Examples of trifunctional or higher hydroxycarboxylic acids include malic acid, hydroxyglutaric acid, hydroxymethylglutaric acid, tartaric acid, citric acid, hydroxyisophthalic acid, and hydroxyterephthalic acid. One of these may be used alone, or two or more may be used in any combination and ratio.

When the polyester resin (A) or polyester resin (B) contains a structural unit derived from a compound having a trifunctional or higher functional group, the content is preferably large in terms of easily improving the strain hardening property, but on the other hand , the polyester of the present embodiment is appropriately crosslinked, the strand is easily pulled out stably, and the moldability, mechanical properties, etc. are likely to be good, so the amount is preferably small. Therefore, the content thereof is usually 5 mol% or less, particularly preferably 4 mol% or less, particularly preferably 3 mol% or less, relative to the total 100 mol% of all structural units constituting the polyester. Binary polyesters with no components are most preferred.

<Chain extender>
A chain extender such as a carbonate compound, a diisocyanate compound, a dioxazoline, or a silicate ester may be used in the production of the polyester resin (A) or the polyester resin (B). For example, polyester carbonate can be obtained by using a carbonate compound such as diphenyl carbonate in an amount of preferably 20 mol% or less, more preferably 10 mol% or less, relative to 100 mol% of the total structural units of the polyester. can.

In this case, specific examples of carbonate compounds include diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, ethylene carbonate, and diamyl carbonate. carbonate, dicyclohexyl carbonate and the like. In addition, carbonate compounds composed of the same or different hydroxy compounds derived from hydroxy compounds such as phenols and alcohols can also be used.

Further, specific diisocyanate compounds include 2,4-tolylene diisocyanate, a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, and 1,5-naphthylene diisocyanate. , xylylene diisocyanate, hydrogenated xylylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate.

Specific examples of silicate esters include tetramethoxysilane, dimethoxydiphenylsilane, dimethoxydimethylsilane, and diphenyldihydroxysilane. Any one of these may be used alone, or two or more thereof may be used in any combination and ratio.

<Terminal blocking agent>
Further, in this embodiment, the terminal groups of the polyester may be blocked with carbodiimide, epoxy compound, monofunctional alcohol, carboxylic acid, or the like. When a terminal blocking agent is used, the content thereof is preferably 20 mol % or less, more preferably 10 mol % or less, relative to 100 mol % of the total structural units of the polyester.

In this case, examples of the carbodiimide compound as the terminal blocking agent include compounds having one or more carbodiimide groups in the molecule (including polycarbodiimide compounds). Specifically, the monocarbodiimide compounds include dicyclohexylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, t-butylisopropylcarbodiimide, diphenylcarbodiimide, di-t-butylcarbodiimide, di-β-naphthylcarbodiimide, N, and N'-di-2,6-diisopropylphenylcarbodiimide. Any one of these may be used alone, or two or more thereof may be used in any combination and ratio. Incidentally, in the production of the polyester of the present embodiment, in the same manner as the polyester composition of the present embodiment, which will be described later, various additives such as heat stabilizers, antioxidants, hydrolysis agents, as long as the properties are not impaired. An inhibitor, a crystal nucleating agent, a flame retardant, an antistatic agent, a release agent, an ultraviolet absorber, and the like may be used.

(Raw material for polyester resin (A) and raw material for polyester resin (B))
Raw materials used for producing the polyester resin (A) and the polyester resin (B) may be petroleum-derived raw materials or biomass-derived raw materials. From the viewpoint of environmental protection, it is preferable to use a biomass-derived raw material, and it is more preferable to use a biomass-derived raw material as the main structural unit. Raw materials derived from biomass include dicarboxylic acid components such as 2,5-furandicarboxylic acid, succinic acid, glutaric acid, adipic acid, and sebacic acid, 1,3-propanediol, 1,4-butanediol, 1,2- Examples include diol components such as ethanediol.

(Physical properties of polyester resin (A))
The polyester resin (A) preferably has an intrinsic viscosity of 0.60 dl/g or more and 1.30 dl/g or less measured by the following method. Moreover, it is preferable that the glass transition temperature is 50° C. or higher and 150° C. or lower. 0.25 g of polyester is dissolved in 50 ml of a mixed solvent of phenol/1,1,2,2-tetrachloroethane=50/50 (weight ratio), and measured at 30° C. using an Ubbelohde viscometer. 32.

<Intrinsic viscosity>
The polyester resin (A) particularly preferably has an intrinsic viscosity of 0.70 dl/g or more, particularly preferably 0.75 dl/g or more, most preferably 0.80 dl/g or more. Also, it is preferably 1.50 dl/g or less, more preferably 1.30 dl/g or less. That is, the intrinsic viscosity of the polyester resin (A) is preferably 0.70 dl/g or more and 1.50 dl/g or less. By setting the intrinsic viscosity within such a range, it is suitable for bottle and film molding.

<Glass transition temperature (Tg)>
The glass transition temperature of the polyester resin (A) is preferably 50°C or higher and 150°C or lower. More preferably, the glass transition temperature is 60° C. or higher. On the other hand, it is more preferable that the temperature is 130° C. or lower. Since the glass transition temperature of polyester is within the range described above, even if the content of the bottle is a foaming substance such as carbonated water, deformation due to the pressure difference between the inside and outside of the bottle is unlikely to occur, and the bottle can be stored in a high temperature environment. Even if you save it with , it will be difficult to deform. The glass transition temperature can be measured by the method of JIS K7121-1987 using a differential scanning calorimeter. Specifically, the polyester is heated from 25°C to the melting point +30 to 60°C, then lowered to 25°C, and then raised again to the melting point +30 to 60°C. Here, the rate of temperature increase and the rate of temperature decrease are set to 10° C./min. The midpoint glass transition temperature in this second temperature rise is taken as the glass transition temperature.

(Physical properties of polyester resin (B))
The polyester resin (B) preferably has an intrinsic viscosity of 0.70 dl/g or more and 1.50 dl/g or less. Moreover, it is preferable that the glass transition temperature is 50° C. or higher and 150° C. or lower.

<Intrinsic viscosity>
The polyester resin (B) particularly preferably has an intrinsic viscosity of 0.70 dl/g or more, particularly preferably 0.80 dl/g or more, and most preferably 1.00 dl/g or more. Also, it is preferably 1.50 dl/g or less, more preferably 1.30 dl/g or less. That is, the intrinsic viscosity of the polyester resin (B) is preferably 0.70 dl/g or more and 1.50 dl/g or less. By setting the intrinsic viscosity within such a range, a polyester having both excellent stretchability and creep resistance can be obtained. When the intrinsic viscosity is within the above range, it becomes easy to obtain a molded article having excellent strain hardening property, small unevenness in thickness, and good creep resistance and impact resistance. In addition, the use of the polyester resin (B) makes it possible to reduce the weight of the bottle by using the polyester resin (B), which reduces unevenness in thickness and enables a uniform thin film, thereby reducing the burden on the environment. Furthermore, it is easy to extrude without applying high pressure during molding.

The reason why the strain hardening property of polyester is likely to occur due to its high intrinsic viscosity is presumed as follows. Strain hardening is a phenomenon in which the viscosity of a resin increases more than the linear viscosity depending on the drawing speed. Normally, in the stretching process, stress is concentrated on a thin portion of the film, causing deformation to progress, and thickness unevenness tends to increase. However, even if the polymer having strain hardening property is stretched, the viscosity becomes high at the thinned portion, so the thickness tends to be uniform, and it is suitable for the stretch molding process.

<Glass transition temperature (Tg)>
The glass transition temperature of the polyester resin (B) is preferably 50°C or higher and 150°C or lower. More preferably, the glass transition temperature is 60° C. or higher. On the other hand, it is more preferable that the temperature is 130° C. or lower. Since the glass transition temperature of polyester is within the range described above, even if the content of the bottle is a foaming substance such as carbonated water, deformation due to the pressure difference between the inside and outside of the bottle is unlikely to occur, and the bottle can be stored in a high temperature environment. Even if you save it with , it will be difficult to deform.

As the method for producing the polyester of the present embodiment, a known method for producing a polyester resin can be employed. Moreover, the reaction conditions at this time are not particularly limited, and any suitable conditions that have been conventionally employed can be set.

Specifically, a dicarboxylic acid component containing 2,5-furandicarboxylic acid as an essential component, an aliphatic diol component preferably containing 1,2-ethanediol, other copolymer components used as necessary, etc. can be produced by carrying out an esterification reaction or a transesterification reaction step using and subsequently carrying out a polycondensation reaction step. In addition, the esterification reaction or transesterification reaction step and the polycondensation reaction step are also referred to as a polyester production step. In the reaction, if necessary, the aforementioned chain extender or terminal blocking agent may be used. Further, in order to increase the intrinsic viscosity, it is preferable to perform the solid phase polymerization step after performing the polycondensation reaction step in the polyester production process.

(Mixing ratio of polyester resin (A) and polyester resin (B) in masterbatch for bottle molding)
In the masterbatch according to the present embodiment, the content of the polyester resin (B) determined by (Equation 1) is 90% by mass or less. It is also conceivable to carry out blend molding of the polyester resin (A) and the polyester resin (B) without using a masterbatch to adjust the content of the polyester resin (B) in the blend molded product to a desired content. However, when molding 100% PET resin as the polyester resin (A) into a preform, the polyester resin (A ) and the polyester resin (B) are blend-molded, the compatibilization of the polyester resin (A) and the polyester resin (B) becomes insufficient, and the appearance of the preform becomes white. If the cycle time is made longer than the reference cycle time in order to suppress whitening of the preform, the productivity of the preform is lowered. In order to solve such problems, the masterbatch and the polyester resin (A) are blend-molded to adjust the content of the polyester resin (B) in the blend-molded product to a desired content. However, in the masterbatch according to the present embodiment, when the content of the polyester resin (B) obtained by (Equation 1) exceeds 90% by mass, whitening is observed in the appearance of the preform blend-molded at the reference cycle time. and sufficient transparency cannot be obtained. The cycle time can be shortened by setting the content of the polyester resin (B) determined by (Equation 1) to 90% by mass or less. Furthermore, by setting the amount to 70% by mass or less, it is possible to obtain a molded product in which the polyester resin (A) and the polyester resin (B) are sufficiently compatible under the molding conditions and cycle time of 100% PET resin.

In the masterbatch according to the embodiment, it is preferable that the content of the polyester resin (B) determined by (Equation 1) is 45% by mass or more. It is possible to achieve both high productivity and high quality of molded products. When the content of the polyester resin (B) obtained by (Equation 1) is less than 45% by mass, the polyester resin (A) and the polyester resin (B) are mixed at the same cycle time as the molding conditions of 100% PET resin. Although a sufficiently compatible molded product can be obtained, when the masterbatch and the polyester resin (A) are blend-molded, it is necessary to reduce the blending ratio of the polyester resin (A) and increase the blending ratio of the masterbatch. Therefore, many masterbatches must be prepared, and the burden of inventory management increases. As a result, the preform production efficiency may decrease.

Similar to preforms, when molding a film, the use of a masterbatch promotes compatibility between the polyester resin (A) and the polyester resin (B) and suppresses whitening of the film. The content of the polyester resin (B) in the masterbatch is preferably 45-90% by weight, more preferably 45-80% by weight, and even more preferably 45-70% by weight. By setting the above range, if it is less than the above, the content of the polyester (B) in the masterbatch will be low, and it will be difficult to increase the content of the polyester (B) in the film, making it impossible to achieve the desired physical properties. be. When the above is exceeded, sufficient transparency may not be obtained.

The masterbatch according to the present embodiment preferably has an intrinsic viscosity (IV value) measured according to (Condition 1) of 0.50 dl/g or more and 1.20 dl/g or less.
(Condition 1) 0.25 g of the masterbatch is dissolved in 50 ml of a mixed solvent of phenol/1,1,2,2-tetrachloroethane = 50/50 (weight ratio), and measured at 30°C using an Ubbelohde viscometer. The Huggins constant is 0.32. If the intrinsic viscosity (IV value) measured according to (Condition 1) is less than 0.50 dl/g, the mechanical properties of the molded product may be insufficient. On the other hand, when the intrinsic viscosity (IV value) exceeds 1.20 dl/g, molding may become difficult.

The masterbatch according to this embodiment includes being for molding pressure-resistant bottles, bottles for heated sales, or heat-resistant bottles. A container obtained by blending a PET resin with a PEF resin is expected to have high mechanical strength and barrier properties, and is suitable for a pressure-resistant bottle, a heated bottle, or a heat-resistant bottle. However, if the compatibility is insufficient, the appearance will whiten. Therefore, it is preferable that the whitening is suppressed for a container for which transparency is preferred. A container obtained by blending PET resin with PEF resin using the masterbatch according to the present embodiment can obtain transparency in the same molding time as PET resin.

The masterbatch according to the present embodiment satisfies that the content of the polyester resin (B) obtained by (Equation 1) is 90% by mass or less, and the polyester resin (A) and the A thermoplastic resin other than the polyester resin (B) can be contained. However, from the viewpoint of ensuring the content of the polyester resin (B) in the blow-molded bottle, the total mass of the polyester resin (A) and the polyester resin (B) is preferably 50% or more with respect to the total mass of the masterbatch. is 80% or more, more preferably 100%.

<Thermoplastic resin other than polyester resin (A) and polyester resin (B) contained in masterbatch>
Thermoplastic resins other than polyester resin (A) and polyester resin (B) (hereinafter also referred to as other thermoplastic resin 1) to be contained in the masterbatch include polyester resin (A) and polyester resin (B) other than Examples thereof include polyester (hereinafter also referred to as other polyester 1), crosslinkable thermoplastic resin, acryl, polycarbonate, and the like. Among these, at least one of the other polyester 1 and the crosslinkable thermoplastic resin is preferable in terms of excellent strain hardening property. Other thermoplastic resins 1 may be used alone, or two or more of them may be used in any combination and ratio.

<Other Polyester 1>
Another polyester 1 is a polyester having a diol-derived structural unit and a dicarboxylic acid-derived structural unit, and is a polyester other than the polyester resin (A) and the polyester resin (B). Examples of dicarboxylic acids constituting dicarboxylic acid units of other polyesters include o-phthalic acid, isophthalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, octylsuccinic acid, cyclohexanedicarboxylic acid, naphthalenedicarboxylic acid, fumaric acid, maleic acid, itaconic acid, decamethylenecarboxylic acid, their anhydrides and lower alkyl esters.

On the other hand, examples of the diol constituting the diol unit possessed by the other polyester 1 include 1,3-propanediol, 1,4-butanediol, diethylene glycol, 1,5-pentanediol, 1,6-hexanediol, di propylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-butanediol, 2,3-butanediol, neopentyl glycol (2,2-dimethylpropane-1,3-diol), 1,2-hexanediol, 2,5-hexanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, polytetramethylene Chain diols such as glycol; alkylene oxides of 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 2,2-bis(4-hydroxycyclohexyl)propane, and 2,2-bis(4-hydroxycyclohexyl)propane Aliphatic diols such as cyclic diols such as adducts and the like are included.

<Crosslinkable thermoplastic resin>
The strain hardening property can also be improved by jointly using a crosslinkable thermoplastic resin having a functional group capable of reacting with the carboxyl group or hydroxyl group contained in the masterbatch. Examples of functional groups capable of reacting with carboxyl groups and hydroxyl groups include epoxy groups, oxazoline groups, carboxyl groups, and carbodiimide groups. These functional groups are preferably on the side chains of the thermoplastic resin. When these functional groups are present in the side chains, a branched structure is formed, which delays the relaxation of molecular extension during stretch molding, thereby improving the strain hardening property.

Thermoplastic resins other than the polyester resin (A) and the polyester resin (B) contained in the masterbatch are not included in the masterbatch, and the masterbatch and the polyester resin (A) are blended to form a preform. They may be added at the same time and blended together.

<Additives to be included in the masterbatch>
In the production of the masterbatch, various additives such as heat stabilizers, antioxidants, hydrolysis inhibitors, crystal nucleating agents, flame retardants, antistatic agents, release agents, An ultraviolet absorber or the like may be used.

These additives may be added to the reactor before the polyester polymerization reaction, may be added to the conveying device or the like from the start of the polymerization reaction to before the end of the polymerization reaction, or may be added to the product after the end of the polymerization reaction. may be added before extraction. Alternatively, it may be added to the product after extraction.

Also, during the production of the masterbatch, in addition to the various additives described above, an impact resistance modifier, a crystal nucleating agent, a reinforcing agent, an extender, a bluing agent, etc. may be added and molded. When an additive or the like is used, one type may be used alone, or two or more types may be used in any combination and ratio.

Additives, impact modifiers, crystal nucleating agents, reinforcing agents, extenders, bluing agents, etc. are not included in the masterbatch, and the masterbatch and the polyester resin (A) are blended to form a preform. may be added during molding and blended together.

<Impact modifier>
The masterbatch may contain impact modifiers for later molding into preforms. By containing the impact modifier, the mechanical properties of the preform can be improved. When the impact modifier is included, the content thereof is preferably 0.01% by weight or more and 10% by weight or less based on the mass of the preform. Examples of impact modifiers include butadiene-based rubbers, acrylic-based rubbers, silicone-acrylic composite rubbers, and the like. Among them, core-shell type impact modifiers such as Metabrene (manufactured by Mitsubishi Chemical Corporation) and Kaneace (manufactured by Kaneka Corporation) are preferably used.

A filler may be used in the production of the masterbatch. The filler may be inorganic or organic. The content of the filler may be selected within a range in which the effect of addition of the filler is sufficiently obtained and the tensile elongation and impact resistance of the preform are maintained, based on the preform. Inorganic fillers include anhydrous silica, mica, talc, titanium oxide, calcium carbonate, diatomaceous earth, allophane, bentonite, potassium titanate, zeolite, sepiolite, smectite, kaolin, kaolinite, glass, limestone, carbon, and wollastonite. , calcined perlite, calcium silicate, silicates such as sodium silicate, hydroxides such as aluminum oxide, magnesium carbonate, calcium hydroxide, salts such as ferric carbonate, zinc oxide, iron oxide, aluminum phosphate, barium sulfate, etc. is mentioned.

In the case of a preform containing an inorganic filler, the content in the preform is usually 1% by weight or more, preferably 3% by weight or more, and more preferably 5% by weight or more. Also, it is usually 80% by weight or less, preferably 70% by weight or less, and more preferably 60% by weight or less.

Organic fillers include raw starch, modified starch, pulp, chitin/chitosan, coconut shell powder, bamboo powder, bark powder, kenaf and straw powder, and the like. Also, nanofiber cellulose obtained by defibrating fibers such as pulp to a nano level can be used.

In the case of a preform containing an organic filler, the content in the preform is usually 0.1% by weight or more, preferably 1% by weight or more. Moreover, it is usually 70% by weight or less, preferably 50% by weight or less.

Crystal nucleating agents include glass fiber, carbon fiber, titanium whisker, mica, talc, boron nitride, CaCO ₃ , TiO ₂ , silica, layered silicate, polyethylene wax, polypropylene wax, etc. Talc, boron nitride, Silica, layered silicate, polyethylene wax and polypropylene wax are preferred, and talc is particularly preferred.

In addition, inorganic fillers added to improve the rigidity of the preform and organic stabilizers added as heat stabilizers may also contribute to the promotion of crystallization. In addition, foreign matter such as inorganic substances or organic substances mixed in during the manufacturing process or molding process of polyester can also serve as a crystal nucleating agent. Accordingly, the term "crystal nucleating agent" as used herein refers to particles that are solid at room temperature and contribute to the promotion of crystallization.

The particle size of the crystal nucleating agent is preferably small. The grain size of the crystal nucleating agent is preferably 5 μm or less, more preferably 3 μm or less, still more preferably 1 μm or less, and most preferably 0.5 μm or less. The lower limit of the grain size of the crystal nucleating agent is usually 0.1 μm.

When a crystal nucleating agent is used in the production of the preform, its amount is preferably 0.001% by weight or more, more preferably 0.01% by weight or more, and still more preferably 0.1% by weight, based on the mass of the preform. % or more. The upper limit of the amount of the crystal nucleating agent is preferably 30% by weight, more preferably 10% by weight, still more preferably 5% by weight, particularly preferably 1% by weight, based on the mass of the preform. By setting the amount of the crystal nucleating agent within the above range, the effect of promoting crystallization is likely to be exhibited, and mechanical properties and flexibility of the preform tend to be obtained.

<Bluing agent>
The masterbatch may further contain a bluing agent. By adding a bluing agent, it is easy to control b* to 2 or less when a bottle is molded.

[Manufacturing method of masterbatch]
A known method can be employed for the production of the masterbatch of the present embodiment. For example, it can be produced by melt-kneading each raw material using a single-screw or twin-screw extruder, Banbury mixer, or the like, and pelletizing.

<Confirmation method of composition>
The composition of the masterbatch can be confirmed by a conventionally known method. For example, after separating the composition into constituent components by HPLC (high performance liquid chromatography), each component is analyzed by NMR (nuclear magnetic resonance spectroscopy), or after methanol decomposition, GC/MS (gas chromatography mass spectrometry) or the like. It can be confirmed by analyzing by

[preform]
The preform according to the present embodiment comprises a polyester resin (A) having a structural unit (A-1) derived from terephthalic acid and a structural unit (A-2) derived from an aliphatic diol, and 2,5-furandicarboxylic A polyester resin containing a structural unit (B-1) derived from an acid and a polyester resin (B) having a structural unit (B-2) derived from 1,2-ethanediol, and obtained by (Equation 1) 1. A bottle preform made of a resin composition containing 5 to 25% by mass of (B) and having an intrinsic viscosity (IV value) of 0.65 dl/g or more as measured according to (Condition 2). 00 dl/g or less, and the haze value measured according to JIS K 7136:2000 "Plastics - Determining the haze of transparent materials" is 0.1 to 8.0%, except that the luminous flux is focused to 7.0 mm square. is. The content of the polyester resin (B) determined by (Equation 1) is preferably 5 to 15% by mass, more preferably 5 to 10% by mass. The intrinsic viscosity (IV value) measured according to (Condition 2) is preferably 0.65 dl/g or more and 0.95 dl/g or less, more preferably 0.70 dl/g or more and 0.90 dl/g or less. The haze value is preferably 0.1-6.0%, more preferably 0.1-3.0%.
(Formula 1) content of polyester resin (B) (% by mass) = content of polyester resin (B) / (content of polyester resin (A) + content of polyester resin (B))
(Condition 2) 0.25 g of a sample cut from the preform was dissolved in 50 ml of a mixed solvent of phenol/1,1,2,2-tetrachloroethane = 50/50 (weight ratio), and measured at 30°C using an Ubbelohde viscometer. , and the Huggins constant is 0.32.

Here, in the method for producing a molded article according to the present embodiment, the masterbatch is a masterbatch in which the content of the polyester resin (B) obtained by (Equation 1) is 45% by weight to 90% by weight, and A mode in which the step of molding a molded article is a step of molding a preform for a bottle by blending the masterbatch and the polyester resin (A) is included.

That is, the masterbatch according to the present embodiment, the polyester resin (A), and other additives used as necessary are directly melt-kneaded during injection molding, and then injected into the mold in a molten state, cooled, and taken out. to form a preform. In this embodiment, as a masterbatch, a twin screw is provided in order to use pellets obtained by blending the polyester resin (A) and the polyester resin (B) and pellets of the polyester resin (A) as raw materials for molding. Even if the polyester resin (A) and the polyester resin (B) in the preform are sufficiently compatible with each other, even if the preform is formed by direct melt-kneading during injection molding using an injection molding machine or the like. Although the resin temperature in this extrusion step is not particularly limited, it is usually in the range of 210 to 290° C., preferably 230 to 270° C., from the standpoint of moldability and suppression of thermal deterioration. For example, in the case of an injection molding machine equipped with twin screws, the melt-kneading time is 120 seconds or more and 300 seconds or less, which corresponds to the passage time between the twin screws when molding the preform. In the manufacturing method, it is possible to mold a preform in which whitening is suppressed by compatibilization in the same cycle time as a PET preform.

[Blow molding bottle]
The blow-molded bottle according to the present embodiment comprises a polyester resin (A) having a structural unit (A-1) derived from terephthalic acid and a structural unit (A-2) derived from an aliphatic diol, and a 2,5-flange A polyester containing a structural unit (B-1) derived from a carboxylic acid and a polyester resin (B) having a structural unit (B-2) derived from 1,2-ethanediol, and obtained by (Equation 1) A blow-molded bottle made of a resin composition having a resin (B) content of 5 to 25% by mass, and having an intrinsic viscosity (IV value) measured according to (Condition 3) of 0.65 dl/g or more and 1.00 dl. /g or less, and the haze value measured according to JIS K 7136:2000 "Plastics - Determination of haze of transparent materials" is 0.1 to 20%, except that the luminous flux is focused to 7.0 mm square. The content of the polyester resin (B) determined by (Equation 1) is preferably 5 to 15% by mass, more preferably 5 to 10% by mass. The intrinsic viscosity (IV value) measured according to (Condition 3) is preferably 0.65 dl/g or more and 0.95 dl/g or less, more preferably 0.70 dl/g or more and 0.90 dl/g or less. The haze value is preferably 0.1-10.0%, more preferably 0.1-5.0%.
(Formula 1) content of polyester resin (B) (% by mass) = content of polyester resin (B) / (content of polyester resin (A) + content of polyester resin (B))
(Condition 3) 0.25 g of a sample cut from a blow-molded bottle was dissolved in 50 ml of a mixed solvent of phenol/1,1,2,2-tetrachloroethane = 50/50 (weight ratio), and measured at 30 using an Ubbelohde viscometer. The Huggins constant, measured in °C, is taken to be 0.32.

Here, the method for manufacturing a blow-molded bottle according to this embodiment has a step of blow-molding the preform obtained by the method for manufacturing a molded body according to this embodiment to mold a bottle.

That is, in the blow molding process, the preform is put into a mold of a desired shape heated to a predetermined temperature by a heater, and then high-pressure air is blown into the mold to mount the preform on the mold to form a bottle. The heating temperature of the preform is preferably 90°C to 150°C, more preferably 100°C to 140°C, and particularly preferably 110°C to 130°C. By heating the preform within the above range and blowing in high-pressure air, the thickness of the bottle can be made uniform in blow molding.

The blow-molded bottle according to this embodiment is preferably a pressure-resistant bottle for filling with a carbonate-containing liquid. The blow-molded bottle according to this embodiment has excellent pressure resistance and heat resistance, and is suitable for filling with a carbonate-containing liquid.

The blow-molded bottle according to the present embodiment is preferably a bottle for filling hot beverages, a bottle for hot sale for filling at a high temperature, or a heat-resistant bottle. The blow-molded bottle according to this embodiment has excellent heat resistance and high gas barrier properties, and deformation of the container during hot sale _is suppressed. reduction in volume can be realized. In addition, recyclability is also improved.

The beverage product according to this embodiment is characterized by filling the molded bottle according to this embodiment with a beverage.

Blow-molded bottles can have various shapes depending on the shape of the mold used. The shape of the blow-molded bottle is not particularly limited as long as it can hold a beverage as long as it is for a beverage. In particular, it is suitable for carbonic acid-containing liquids such as carbonated beverages such as beer and champagne, and hot beverages such as tea and coffee, by molding into an appropriate shape with a uniform and sufficiently thick wall thickness.

When these liquids are filled into a bottle, the mouth of the bottle is usually sealed with a resin cap or the like, and the pressure inside the bottle (internal pressure) is higher than the outside of the bottle. Therefore, it is preferable that the bottom of the bottle has a pressure-resistant shape that suppresses deformation due to the internal pressure in order to box, transport, display in a store, etc. in an upright state under high internal pressure. Since the deformation of the bottom and body of the bottle is generally accompanied by a creep (irreversible deformation due to continuous stress) phenomenon, there is commonality in wall thicknesses and shapes suitable for these bottles. Therefore, hereinafter, a bottle used for filling a carbonated liquid, a hot beverage, or the like may be referred to as a "heat-resistant and pressure bottle". That is, the blow-molded bottle of this embodiment is suitable for a heat-resistant and pressure-resistant bottle.

The pressure-resistant shape of the bottom of the heat and pressure bottle can be, for example, a petaloid shape, a so-called champagne bottom shape with a dome shape facing the inside of the container, or a shape with unevenness in the center of the bottom surface. If the average wall thickness is large, deformation and bursting of the bottle due to internal pressure are less likely to occur. Specifically, depending on the internal pressure, the average wall thickness of the bottle body is preferably 0.20 mm or more, more preferably 0.25 mm or more, and even more preferably 0.30 mm or more. The average wall thickness, on the other hand, is also preferably 0.70 mm or less from the standpoint of bottle moldability.

The blow-molded bottle according to the present embodiment has less unevenness in wall thickness and can be uniformly thinned, so that a lightweight heat-resistant and pressure-resistant bottle can be obtained. Specifically, the weight/content of the bottle is preferably 10 g/L or more, more preferably 20 g/L or more, still more preferably 30 g/L or more, and particularly preferably 50 g/L or more. /L or less is preferable, 150 g/L or less is more preferable, and 120 g/L or less is particularly preferable.

In addition, the blow-molded bottle according to the present embodiment is a uniform thin-walled bottle with excellent gas barrier properties, and is particularly suitable as a pressure-resistant bottle for filling carbonated liquids such as carbonated beverages. Moreover, the blow-molded bottle according to the present embodiment is excellent in creep resistance and impact resistance when filled with a carbonated liquid. Specifically, it is preferable as a bottle for filling a liquid containing 1 to 10 GV of carbon dioxide, more preferably as a bottle for filling a liquid containing 1 to 5 GV of carbon dioxide, and a liquid containing 1 to 3 GV of carbon dioxide. It is more preferable as a filling bottle for , and particularly preferable as a filling bottle for a liquid containing 1 to 2 GV of carbon dioxide gas.

The blow-molded bottle according to this embodiment has excellent oxygen barrier properties. Suitable for alcoholic beverages such as wine bottles. In particular, since the gas barrier property is superior to that of conventional PET bottles for alcoholic beverages, shelf life can be extended without using other means for improving gas barrier property such as multi-layer molding or coating. When the resin composition of the blow-molded bottle according to the present embodiment has a glass transition temperature of 50° C. or higher, deformation due to the pressure difference between the inside and outside of the bottle is less likely to occur. be. In addition, since it does not easily deform even when stored in a high-temperature environment, it is suitable for pressure-resistant bottles that are filled at high temperatures and hot beverage bottles that are heated and sold.　

In this embodiment, a preform with suppressed whitening can be obtained in spite of having a preform molding cycle time equivalent to that of a PET bottle, and whitening is suppressed in a bottle obtained by blow molding it. .

[the film]
The film according to the present embodiment comprises a polyester resin (A) having a structural unit (A-1) derived from terephthalic acid and a structural unit (A-2) derived from an aliphatic diol, and 2,5-furandicarboxylic acid. A polyester resin (B) having a structural unit (B-1) derived from 1,2-ethanediol and a structural unit (B-2) derived from 1,2-ethanediol, and a polyester resin obtained by (Equation 1) ( A film made of a resin composition in which the content of B) is 1 to 90% by mass, and the intrinsic viscosity (IV value) measured according to (Condition 4) is 0.50 dl / g or more and 1.00 dl / g or less The haze value measured according to JIS K 7136:2000 "Plastics - Determination of haze of transparent materials" is 0.01 to 6.0%, except that the luminous flux is narrowed to 7.0 mm square. In addition, in this embodiment, the "film" includes an article generally called a "sheet".
(Formula 1) content of polyester resin (B) (% by mass) = content of polyester resin (B) / (content of polyester resin (A) + content of polyester resin (B))
(Condition 4) 0.25 g of a sample cut from the film was dissolved in 50 ml of a mixed solvent of phenol/1,1,2,2-tetrachloroethane = 50/50 (weight ratio), and measured at 30°C using an Ubbelohde viscometer. The measured Huggins constant is 0.32.

The content of the polyester resin (B) in the film is preferably 1-90% by mass, more preferably 20-90% by mass, and most preferably 40-90% by mass. By setting it as said range, a film with high transparency, gas-barrier property, and surface hardness can be obtained.

The haze value of the film is preferably 0.01-6.0%, more preferably 0.01-4.5%, and most preferably 0.01-1.5%. By setting it as these ranges, it can be used suitably for the uses which require high transparency, such as an optical use.

Here, the method for producing a film according to this embodiment has a step of blending the masterbatch according to this embodiment and the polyester resin (A) to form a film. That is, the masterbatch according to the present embodiment, the polyester resin (A), and other additives used as necessary are directly melt-kneaded during injection molding, and then injected into a mold in a molten state and cooled. to form a film. In this embodiment, as a masterbatch, a twin screw is provided in order to use pellets obtained by blending the polyester resin (A) and the polyester resin (B) and pellets of the polyester resin (A) as raw materials for molding. Even if the film is formed by direct melt-kneading during molding using an extruder or the like, the polyester resin (A) and the polyester resin (B) are sufficiently compatible in the film. The resin temperature in this extrusion step is not particularly limited, but it is usually in the range of 200 to 300° C., preferably 240 to 280° C., from the standpoint of moldability and suppression of thermal deterioration.

The film according to the present embodiment can also be made into a biaxially stretched film with excellent mechanical properties by being biaxially stretched.

A conventionally known method can be used as a method for producing a biaxially stretched film. The following methods are mentioned.

Using a masterbatch and other raw materials, the melted film extruded from the die is cooled and solidified with a cooling roll to obtain an unstretched film. In this case, it is necessary to increase the adhesion between the film and the rotary cooling drum in order to improve the flatness of the film, and the electrostatic application adhesion method and/or the liquid coating adhesion method are preferably employed. The resulting unstretched film is then biaxially stretched. In that case, first, the unstretched film is stretched in one direction by a roll or tenter type stretching machine. The stretching temperature is usually 80 to 140° C., preferably 85 to 120° C., and the stretching ratio is usually 2.5 to 7 times, preferably 3.0 to 6 times. Next, the stretching temperature perpendicular to the stretching direction in the first stage is usually 70 to 170° C., and the stretching ratio is usually 3.0 to 7 times, preferably 3.5 to 6 times. Subsequently, heat treatment is performed at a temperature of 160 to 240° C. under tension or under relaxation within 30% to obtain a biaxially oriented film. In the stretching, a method of stretching in one direction in two or more stages can also be employed. In that case, it is preferable that the stretching ratios in the two directions finally fall within the above ranges.

A simultaneous biaxial stretching method can also be adopted in the production of the biaxially stretched film. The simultaneous biaxial stretching method is a method in which the above unstretched film is stretched simultaneously in two directions while the temperature is controlled at usually 70 to 120°C, preferably 80 to 110°C. The draw ratio is preferably 4 to 50 times, more preferably 7 to 35 times, still more preferably 10 to 25 times in terms of area magnification. Subsequently, heat treatment is performed at a temperature of 160 to 240° C. under tension or under relaxation of 30% or less to obtain a stretched and oriented film. Conventionally known stretching methods such as a screw method, a pantograph method, a linear drive method, and the like can be employed for the simultaneous biaxial stretching apparatus that employs the above-described stretching method.

In the case of applying a so-called application stretching method (in-line coating), in which the film surface is subjected to a primer treatment or a hard coat treatment during the stretching process of the biaxially stretched film, the film after uniaxial stretching is used for forming a primer layer or a hard coat layer. is applied. When a primer or hard coat layer is provided on the film by a coating and stretching method, coating can be performed simultaneously with stretching, and the thickness of the coating layer can be reduced according to the stretching ratio, making it suitable as a biaxially stretched film. film can be produced.

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.

Evaluation methods in the following examples and comparative examples are as follows.
(1) Intrinsic viscosity of polyester A solution obtained by precisely weighing 0.25 g of a sample to be measured and dissolving it by adding 50 ml of a mixed solvent of phenol/1,1,2,2-tetrachloroethane = 50/50 (weight ratio). was measured at 30° C. using a Uderohde viscosity tube. The Huggins constant was set to 0.32.
(2) Glass transition temperature of polyester The glass transition temperature was measured by the method of JIS K7121-1987 using a differential scanning calorimeter "DSC7000x" (manufactured by Hitachi High-Tech Science Co., Ltd.). Specifically, the temperature of the polyester was raised from 25°C to 280°C, then lowered to 25°C, and then raised to 260°C again. Here, the temperature increase rate and temperature decrease rate were set to 10° C./min. The midpoint glass transition temperature in this second temperature rise was defined as the glass transition temperature.
(3) Melting point of polyester The apex of the melting peak in the second temperature rise measured with the same equipment and conditions as the measurement of the glass transition temperature was defined as the melting point.
(4) Gas barrier property (oxygen permeability)
The oxygen permeability of the blow-molded bottle was measured using an oxygen permeability measuring device (OX-TRAN2/21 manufactured by MODERN CONTROL). The oxygen transmission rate was conditioned at 23°C and 90% RH for 12 hours from the start of the measurement, and the value after 72 hours from the start of the measurement was taken. The oxygen gas barrier properties were evaluated relative to the oxygen permeability of a general-purpose PET bottle (100% general-purpose PET bottle obtained in Reference Example E1 described later) as 1. Specifically, the oxygen permeability of Reference Example E1 was divided by the oxygen permeability of the sample for comparison, and the evaluation was made by a magnification. The oxygen gas barrier property was evaluated as good when the calculated magnification exceeded 1.
(5) Cloudiness (Haze)
Using a haze meter "NDH7000SPII" (manufactured by Nippon Denshoku Co., Ltd.), JIS K 7136: 2000 "Plastics - How to determine the haze of transparent materials" except that the luminous flux was narrowed using a 7.0 mm square integrating sphere mask. ”. The haze value of the preform was measured four times at the body portion 4 cm from the bottom, and the haze value of the blow-molded bottle was measured at the body portion 3 cm from the bottom. In addition, as shown in Fig. 1, the preform was cut in half lengthwise and placed so that the outer surface of the preform was on the integrating sphere side and the center of the width direction of the preform was exposed to the light beam. implemented.
(6) b* value of bottle The degree of coloration of the bottle is indicated by the degree of coloration b* value, which is the color difference in JIS K 7105-1981 “Testing methods for optical properties of plastics”. Colorless is defined as having a b* value of 2.0 or less. The b* value is more preferably 1.7 or less. The b* value can be obtained by Equation (5). Note that X, Y, or Z in Equation 5 are tristimulus values. Further, the correlation between the b* value and visual observation in the present invention is roughly shown in Table 1.

[Production of masterbatch]
(Example A1)
Using KZW15 (manufactured by Technobell Co., Ltd.), polyethylene furanoate (manufactured by Mitsubishi Chemical Corporation, IV = 1.12 dl / g, glass transition point 83 ° C.) as polyester resin (B) and polyethylene terephthalate as polyester resin (A) (Mitsubishi Chemical Indonesia, BK2180, IV = 0.83 dl/g, glass transition point 74°C) were kneaded to prepare a masterbatch. Specifically, the following operations were performed. Polyethylene furanoate pellets and polyethylene terephthalate pellets are weighed so that the content of the polyester resin (B) obtained by (Equation 1) is 50% by mass, and uniformly stirred to form a pellet mixture for preparing a masterbatch. got The obtained pellet mixture was charged into a hopper, kneaded under the following conditions, and a molten resin was obtained from a 2.5 mmφ strand die. The resulting molten resin was directly immersed in a water bath at 23° C. and cooled to form a strand, which was passed through a pelletizer to obtain a masterbatch of polyethylene furanoate and polyethylene terephthalate.
(Formula 1) content of polyester resin (B) (% by mass) = content of polyester resin (B) / (content of polyester resin (A) + content of polyester resin (B))
(Melt-kneading conditions)
Pellets supply rate: 2.0 kg/h
Cylinder temperature C1: 200°C, C2-C8: 280°C
Head temperature: 280°C
Die temperature: 280°C
Screw rotation speed: 250 rpm

(Example A2)
A masterbatch was obtained in the same manner as in Example A1, except that the polyethylene furanoate pellets and the polyethylene terephthalate pellets were weighed so that the content of the polyester resin (B) obtained by (Equation 1) was 60% by mass. rice field.

(Example A3)
A masterbatch was obtained in the same manner as in Example A1, except that the polyethylene furanoate pellets and the polyethylene terephthalate pellets were weighed so that the content of the polyester resin (B) obtained by (Equation 1) was 70% by mass. rice field.

[Manufacture of bottle preforms]
[Example B1]
A bottle preform is prepared by using the masterbatch of Example A1 and polyethylene terephthalate (manufactured by Mitsubishi Chemical Indonesia, BK2180, IV=0.83 dl/g, glass transition point 74° C.) as a polyester resin (A) as raw materials for preforms. manufactured. Specifically, the following operations were performed. The masterbatch pellets and polyethylene terephthalate pellets of Example A1 were weighed so that the content of the polyester resin (B) obtained by (Equation 1) was 10% by mass, and uniformly stirred to obtain a bottle preform. A pellet mixture was obtained for fabrication. The resulting pellet mixture was put into a hopper and injection molded under the following conditions to obtain a bottle preform. The volume was 22.7 ml, the weight was 20 g, and the average wall thickness of the trunk was 2.9 mm.
(Injection molding conditions)
"CLF180" manufactured by CHUAN LIH FA
Melting temperature: 300°C
Injection pressure: 290bar
Cycle time 22 seconds Cooling time 5 seconds

[Example B2]
A bottle preform was obtained in the same manner as in Example B1, except that the masterbatch of Example A2 was used. The volume, weight, and average wall thickness of the trunk portion were the same as in Example B1.

[Example B3]
A bottle preform was obtained in the same manner as in Example B1 except that the masterbatch of Example A3 was used. The volume, weight, and average wall thickness of the trunk portion were the same as in Example B1.

[Comparative Example B1]
Polyethylene furanoate (manufactured by Mitsubishi Chemical Corporation, IV = 1.12 dl / g, glass transition point 83 ° C.) as the polyester resin (B) and polyethylene terephthalate (manufactured by Mitsubishi Chemical Indonesia, BK2180, IV = 0) as the polyester resin (A) .83 dl/g, glass transition point 74° C.) was used as a preform raw material to produce a bottle preform without using a masterbatch. Specifically, the following operations were performed. Polyethylene furanoate pellets and polyethylene terephthalate pellets were weighed so that the content of the polyester resin (B) obtained by (Equation 1) was 10% by mass, and uniformly stirred to prepare a bottle preform. A pellet mixture was obtained. The resulting pellet mixture was put into a hopper and injection molded under the following conditions to obtain a bottle preform. The volume was 22.7 ml, the weight was 20 g, and the average wall thickness of the trunk was 2.9 mm.
(Injection molding conditions)
"CLF180" manufactured by CHUAN LIH FA
Melting temperature: 300°C
Injection pressure: 290bar
Cycle time 22 seconds Cooling time 5 seconds

[Reference Example C1] Production of preform for general-purpose PET 100% bottle Commercially available polyester (polyethylene terephthalate trade name “Novapex BK2180” manufactured by Mitsubishi Chemical Corporation, IV = 0.83 dl / g, glass transition point 74 ° C.) for preform As a raw material, a bottle preform was manufactured. The volume was 22.7 ml, the weight was 20 g, and the average wall thickness of the trunk was 2.9 mm.
(Injection molding conditions)
"CLF180" manufactured by CHUAN LIH FA
Melting temperature: 300°C
Injection pressure: 290bar
Cycle time 22 seconds Cooling time 5 seconds

[Manufacturing of blow-molded bottles]
[Examples D1 to D3, Comparative Example D1, Reference Example E1]
Blow molded bottles of Examples D1 to D3 were obtained by blow molding the preforms of Examples B1 to B3 using a blow molding machine (FRB-1 manufactured by Frontier Corporation). Further, the preform of Comparative Example B1 was similarly blow-molded to obtain a blow-molded bottle of Comparative Example D1. Further, the preform of Reference Example C1 was similarly blow-molded to obtain a blow-molded bottle of Reference Example E1. The blow-molded bottle was a bottle for hot sale having a volume of 280 ml, a weight of 20 g, and an average body thickness of 0.26 mm.

Table 2 shows the obtained evaluation results.

From the results summarized in Table 2, the following was found. Examples D1 to D3 had higher gas barrier properties than Reference Example E1. In addition, Examples D1 to D3 had a lower haze value and b* than Comparative Example D1 in which the cycle time was the same as 22 seconds, and the appearance was good. Therefore, Examples D1 to D3, which passed through the masterbatch, were able to mold bottles with a good appearance while maintaining cycle time equivalent to that of Reference Example E1, that is, ensuring productivity equivalent to that of PET bottles.

Comparing Examples B1 to B3 with Examples D1 to D3, it was found that the haze value and b* increased through blow molding. Therefore, it has been found that it is necessary to produce a preform with a good appearance in order to obtain a bottle with a good appearance.

(Example F1)
Using a small kneader (Xplore series MC15 manufactured by Xplore Instruments), polyethylene furanoate (manufactured by Mitsubishi Chemical Corporation, IV = 1.12 dl / g, glass transition point 83 ° C.) 7.5 g and polyethylene terephthalate (Mitsubishi Chemical GM700Z, IV = 0.84 dl/g, glass transition point 74°C) was supplied from a hopper as a raw material, kneaded for 5 minutes at 100 rpm, 240°C under a nitrogen atmosphere, and then passed through a purge hole. A polyester masterbatch strand was obtained by recovering the resin after kneading. When the resin was recovered, crystallization was suppressed by quenching it with pure water at 23°C. The intrinsic viscosity (IV value) of the resulting masterbatch strand was 0.76 dl/g. Next, 3 g of the obtained masterbatch and 12 g of polyethylene terephthalate, which is the same as the product used to prepare the masterbatch, are kneaded in the same manner as described above to obtain a polyester composition (polyethylene furanoate/polyethylene terephthalate = 10/90% by weight). Got a strand.

(Example F2)
Example F1 except that the amounts of the resins used in the preparation of the masterbatch were 13.5 g of polyethylene furanoate and 1.5 g of polyethylene terephthalate, and the amounts of the resins in the preparation of the polyester composition were set to 1.67 g of the masterbatch and 13.33 g of polyethylene terephthalate. A strand of a polyester composition (polyethylene furanoate/polyethylene terephthalate=10/90% by weight) was obtained in the same manner as above. The intrinsic viscosity (IV value) of the obtained masterbatch strand was 0.82 dl/g.

(Comparative example F1)
1.5 g of polyethylene furanoate (manufactured by Mitsubishi Chemical Corporation, IV = 1.12 dl / g, glass transition point 83 ° C.) and polyethylene terephthalate (manufactured by Mitsubishi Chemical Corporation, GM700Z, IV = 0.84 dl / g, glass transition point 74 ℃) 13.5 g as a raw material is supplied from a hopper, kneaded for 5 minutes under a nitrogen atmosphere at a rotation speed of 100 rpm, 240 ° C., and then the resin after kneading is recovered from the purge hole to obtain a strand of the polyester composition (polyethylene furanoate/polyethylene terephthalate=10/90% by weight).

(Example G1)
A metal frame (SUS304, outer diameter 110 mm, inner diameter 70 mm, thickness 0.2 mm) that has been subjected to surface release treatment is placed on a 150 mm × 150 mm polyimide film (Upilex S, manufactured by Ube Industries, Ltd., thickness 0.05 mm). 2.0 g of the polyester composition obtained in Example F1 was measured on the inside of the tube, and the same polyimide film of 150 mm x 150 mm was placed thereon. With the masterbatch sandwiched between the polyimide films sandwiched between two iron plates (160 mm × 160 mm, thickness 3 mm), a heat press (IMC-180C type manufactured by Imoto Seisakusho Co., Ltd.) is used to heat press. By doing so, a hot press film of 70 mm×70 mm×0.2 mm in thickness was obtained. The hot-pressing temperature was 280° C., and the hot-pressing time was 1 minute for preheating and 1 minute for pressing. The haze of the resulting film was as good as 1.33%. The intrinsic viscosity (IV value) of the resulting film was 0.62 dl/g.

(Example G2)
A heat-pressed film was obtained in the same manner as in Example G1, except that the polyester composition obtained in Example F2 was used. The resulting film had a haze of 4.30%, which was inferior to Example G1, but was better than Comparative Example G1 in which no masterbatch was used. The intrinsic viscosity (IV value) of the resulting film was 0.68 dl/g.

(Comparative example G1)
A heat-pressed film was obtained in the same manner as in Example G1, except that the polyester composition obtained in Comparative Example F1 was used. The obtained film had a haze of 7.27% and was insufficient in transparency. The intrinsic viscosity (IV value) of the resulting film was 0.64 dl/g.

Claims (12)

1. a polyester resin (A) having a structural unit (A-1) derived from terephthalic acid and a structural unit (A-2) derived from an aliphatic diol;
   A polyester resin (B) having a structural unit (B-1) derived from 2,5-furandicarboxylic acid and a structural unit (B-2) derived from 1,2-ethanediol,
   The content of the polyester resin (B) determined by (Equation 1) is 45% by weight to 90% by weight,
   A masterbatch characterized by having an intrinsic viscosity (IV value) measured according to (Condition 1) of 0.50 dl/g to 1.20 dl/g.
   (Formula 1) content of polyester resin (B) (% by mass) = content of polyester resin (B) / (content of polyester resin (A) + content of polyester resin (B))
   (Condition 1) 0.25 g of the masterbatch is dissolved in 50 ml of a mixed solvent of phenol/1,1,2,2-tetrachloroethane = 50/50 (weight ratio), and measured at 30°C using an Ubbelohde viscometer. The Huggins constant is 0.32.
2. The masterbatch according to claim 1, which is for molding pressure-resistant bottles, bottles for heated sales, or heat-resistant bottles.
3. a polyester resin (A) having a structural unit (A-1) derived from terephthalic acid and a structural unit (A-2) derived from an aliphatic diol;
   A polyester resin (B) having a structural unit (B-1) derived from 2,5-furandicarboxylic acid and a structural unit (B-2) derived from 1,2-ethanediol,
   The polyester resin (B) content determined by (Equation 1) is 90% by mass or less, and the intrinsic viscosity (IV value) measured by (Condition 1) is 0.50 dl / g to 1.20 dl / g. A step of making a masterbatch;
   and a step of separately melt-kneading the masterbatch and the polyester resin (A) to form a molded article.
   (Formula 1) content of polyester resin (B) (% by mass) = content of polyester resin (B) / (content of polyester resin (A) + content of polyester resin (B))
   (Condition 1) 0.25 g of the masterbatch is dissolved in 50 ml of a mixed solvent of phenol/1,1,2,2-tetrachloroethane = 50/50 (weight ratio), and measured at 30°C using an Ubbelohde viscometer. The Huggins constant is 0.32.
4. The masterbatch is a masterbatch in which the content of the polyester resin (B) determined by (Equation 1) is 45% by weight to 90% by weight,
   4. The production of the molded article according to claim 3, wherein the step of molding the molded article is a step of blending the masterbatch and the polyester resin (A) to form a preform for a bottle. Method.
5. A method for producing a blow-molded bottle, comprising the step of blow-molding the preform according to claim 4 to form a bottle.
6. a polyester resin (A) having a structural unit (A-1) derived from terephthalic acid and a structural unit (A-2) derived from an aliphatic diol;
   A polyester resin (B) having a structural unit (B-1) derived from 2,5-furandicarboxylic acid and a structural unit (B-2) derived from 1,2-ethanediol,
   A bottle preform made of a resin composition having a polyester resin (B) content of 5 to 25% by mass as determined by (Equation 1),
   (Condition 2) has an intrinsic viscosity (IV value) of 0.65 dl/g or more and 1.00 dl/g or less,
   A preform characterized by having a haze value of 0.1 to 8% as measured according to JIS K 7136:2000 "Plastics - Determination of haze of transparent materials" except that the luminous flux is narrowed to 7.0 mm square. .
   (Formula 1) content of polyester resin (B) (% by mass) = content of polyester resin (B) / (content of polyester resin (A) + content of polyester resin (B))
   (Condition 2) 0.25 g of a sample cut from the preform was dissolved in 50 ml of a mixed solvent of phenol/1,1,2,2-tetrachloroethane = 50/50 (weight ratio), and measured at 30°C using an Ubbelohde viscometer. , and the Huggins constant is 0.32.
   
7. a polyester resin (A) having a structural unit (A-1) derived from terephthalic acid and a structural unit (A-2) derived from an aliphatic diol;
   A polyester resin (B) having a structural unit (B-1) derived from 2,5-furandicarboxylic acid and a structural unit (B-2) derived from 1,2-ethanediol,
   A blow-molded bottle made of a resin composition having a polyester resin (B) content of 5 to 25% by mass as determined by (Equation 1),
   (Condition 3) has an intrinsic viscosity (IV value) of 0.65 dl/g or more and 1.00 dl/g or less,
   Blow molding characterized in that the haze value measured according to JIS K 7136: 2000 "Plastics - Determination of haze of transparent materials" is 0.1 to 20%, except that the luminous flux is narrowed to 7.0 mm square. Bottle.
   (Formula 1) content of polyester resin (B) (% by mass) = content of polyester resin (B) / (content of polyester resin (A) + content of polyester resin (B))
   (Condition 3) 0.25 g of a sample cut from a blow-molded bottle was dissolved in 50 ml of a mixed solvent of phenol/1,1,2,2-tetrachloroethane = 50/50 (weight ratio), and measured at 30 using an Ubbelohde viscometer. The Huggins constant, measured in °C, is taken to be 0.32.
8. The blow-molded bottle according to claim 7, which is a pressure-resistant bottle for filling with a carbonate-containing liquid.
9. The blow-molded bottle according to claim 7, which is a bottle for filling hot sales bottles or a heat-resistant bottle for filling at high temperature.
10. A beverage product characterized by filling the blow-molded bottle according to any one of claims 7 to 9 with a beverage.
11. The method for producing a molded article according to claim 3, wherein the molded article is a film.
12. a polyester resin (A) having a structural unit (A-1) derived from terephthalic acid and a structural unit (A-2) derived from an aliphatic diol;
    A polyester resin (B) having a structural unit (B-1) derived from 2,5-furandicarboxylic acid and a structural unit (B-2) derived from 1,2-ethanediol,
    A film made of a resin composition having a polyester resin (B) content of 1 to 90% by mass as determined by (Equation 1),
    (Condition 4) has an intrinsic viscosity (IV value) of 0.50 dl/g or more and 1.00 dl/g or less,
    The haze value measured according to JIS K 7136: 2000 "Plastics - Determination of haze of transparent materials" is 0.01 to 6.0%, except that the luminous flux is narrowed to 7.0 mm square. the film.
    (Formula 1) content of polyester resin (B) (% by mass) = content of polyester resin (B) / (content of polyester resin (A) + content of polyester resin (B))
    (Condition 4) 0.25 g of the film is dissolved in 50 ml of a mixed solvent of phenol/1,1,2,2-tetrachloroethane = 50/50 (weight ratio), and measured at 30°C using an Ubbelohde viscometer. The constant is 0.32.
    
    

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